WO2017130103A1 - Process for preparing a transition metal-schiff base imine ligand complex - Google Patents
Process for preparing a transition metal-schiff base imine ligand complex Download PDFInfo
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- WO2017130103A1 WO2017130103A1 PCT/IB2017/050369 IB2017050369W WO2017130103A1 WO 2017130103 A1 WO2017130103 A1 WO 2017130103A1 IB 2017050369 W IB2017050369 W IB 2017050369W WO 2017130103 A1 WO2017130103 A1 WO 2017130103A1
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- WIPO (PCT)
- Prior art keywords
- group
- formula
- schiff base
- halide
- transition metal
- Prior art date
Links
- 239000002262 Schiff base Substances 0.000 title claims abstract description 76
- 239000003446 ligand Substances 0.000 title claims abstract description 74
- 230000007704 transition Effects 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 45
- 230000008569 process Effects 0.000 claims abstract description 44
- -1 Schiff base imine Chemical class 0.000 claims abstract description 36
- 239000012530 fluid Substances 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims abstract description 9
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 9
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 150000004820 halides Chemical group 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- 150000002431 hydrogen Chemical class 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000004984 aromatic diamines Chemical class 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011369 resultant mixture Substances 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- ROILLNJICXGZQQ-UHFFFAOYSA-N 3-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC=CC(C=O)=C1O ROILLNJICXGZQQ-UHFFFAOYSA-N 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 62
- 230000009920 chelation Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 231100001261 hazardous Toxicity 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000004753 Schiff bases Chemical class 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229940045348 brown mixture Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
Definitions
- the present disclosure relates to a process for preparing a transition metal-Schiff base imine ligand complex.
- Disentangled ethylene based polymer refers to homo-polymer(s) or copolymer(s) of ethylene having molar mass in the range of 0.1 million to 25 million, crystallinity greater than 75 , heat of melting greater than 180 J/g, and bulk density in the range of 0.03 g/cc to 0.2 g/cc.
- the disentangled ultra-high molecular weight ethylene based polymer is characterized by increase in elastic modulus, represented by a ratio of G'/Go (G'is the elastic modulus at any point in the curve and G° is the initial elastic modulus) with time above the melt temperature when tested on strain controlled rheometer having parallel plate assembly as disentangled polymer chains tend to entangle on application of shearing in sinusoidal test.
- G'/Go G'is the elastic modulus at any point in the curve and G° is the initial elastic modulus
- a representative graph of the change in elastic modulus of the disentangled ultra-high molecular weight ethylene based polymer with time is illustrated in figure 1.
- transition metal-Schiff base imine ligand complexes are used as homogenous catalysts for the production of disentangled ultra-high molecular weight polyethylene.
- the transition metal-Schiff base imine ligand complexes are prepared by the chelation of a Schiff base imine ligand with a transition metal halide. Chelation process involves multiple steps, conventionally uses diethyl ether as the reaction medium (which is hazardous), and/or use of pyrophoric reagents such as n-butyllithium. Chelation involves two steps.
- the Schiff base imine ligand such as phenoxyimine is deprotonated using a base such as n-butyl lithium (which is the most preferred), lithium diisopropylamide, sodium hydride, and potassium hydride, to obtain lithium or sodium salt of phenoxy imines.
- the second step involves reaction of the lithium or sodium salt of the phenoxy imine with a transition metal halide to obtain the transition metal- Schiff base imine ligand complex.
- Chelation steps are associated with various drawbacks such as severe reaction conditions like cooling up to -78° C, using hazardous solvents like diethyl ether, and laborious removal of byproducts from the crude mixture to obtain pure transition metal-Schiff base imine ligand complex. Such severe conditions present a great difficulty in scaling up the transition metal-Schiff base imine ligand complex synthesis process to a commercial level.
- the complex can be prepared by direct addition of phenoxy imine ligands to the transition metal halide that results in imine protonated metal complexes due to generation of hydrogen chloride during the reaction.
- metalation can be carried out in the presence of an organic base such as triethylamine to prevent imine protonation, or the isolated imine protonated metal complexes so formed can be subjected to deprotonation in a subsequent step by adding triethylamine to obtain the desired product.
- Yet another approach involves the use of a [TiCi 4 (THF) 2 ] adduct at -78° C to obtain the metal complexes.
- these processes provide a catalyst with low catalytic productivity. Therefore, there is felt a need to provide a process to prepare the transition metal-Schiff base imine ligand complex using a simple process, and less hazardous reagents.
- An object of the present disclosure is to provide a simple process to prepare a transition metal-Schiff base imine ligand complex.
- the present disclosure relates to a process for preparing a transition metal-Schiff base imine ligand complex.
- the process comprises the following steps.
- each of Rj, R2, R 4 , R6, Rs, Rio, and Rj2 are independently selected from the group consisting of hydrogen, aryl, heteroaryl, and halogen;
- R5, and R are independently selected from tertiary alkyl groups
- R 7 , and Rn are independently selected from the group consisting of hydrogen, and tertiary alkyl group
- R3 is selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl, and sulphonic acid;
- the first product mixture is concentrated under reduced pressure to obtain a first residue comprising a crude Schiff base imine ligand, followed by purification of the first residue to obtain the Schiff base imine ligand, represented by Formula- III.
- the Schiff base imine ligand of Formula-Ill is mixed with a halogenated fluid medium while stirring to obtain a mixture, followed by addition of a transition metal halide to the mixture maintained at a temperature in the range of 20 °C to 40 °C, and stirring the resultant mixture to obtain a second product mixture.
- the second product mixture is concentrated under reduced pressure to obtain a second residue comprising the crude transition metal-Schiff base imine ligand complex, followed by purification of the second residue using an organic fluid medium to obtain the transition metal-Schiff base imine ligand complex, represented by Formula-IV.
- each of R l 5 R 2 , R4, R6, Rs, Rio and R 12 are independently selected from the group consisting of hydrogen, aryl, heteroaryl, and halogen;
- R5, and R are independently selected from tertiary alkyl groups
- R 7 , and Rn are independently selected from the group consisting of hydrogen, and tertiary alkyl group;
- R3 is selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl, and sulphonic acid;
- M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V), and Titanium (Ti); and
- X is a halide selected from the group consisting of CI, Br, and I.
- the aromatic diamine is meta-phenylenediamine.
- the substituted salicylaldehyde of Formula-IIa and the substituted salicylaldehyde of Formula-IIb are independently selected from the group consisting of 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde.
- the substituted salicylaldehyde of Formula-IIa and the substituted salicylaldehyde of Formula-IIb can be same or different.
- the acid catalyst is at least one selected from the group consisting of para-toluene sulfonic acid, and sulfuric acid.
- the first fluid medium is at least one selected from the group consisting of toluene, methanol, ethanol, and xylene.
- the halogenated fluid medium is at least one selected from the group consisting of dichlorome thane, dichloroe thane, carbon tetrachloride, and chloroform.
- the transition metal halide is at least one selected from the group consisting of Hafnium (Hf) halide, Manganese (Mn) halide, Iron (Fe) halide, Rhenium (Re) halide, Tungsten (W) halide, Niobium (Nb) halide, Tantalum (Ta) halide, Vanadium (V) halide and Titanium (Ti) halide; and the halide is selected from the group consisting of chloride, bromide, and iodide.
- the organic fluid medium is at least one selected from the group consisting of n-pentane, n- hexane, n-heptane, n-octane, and n-nonane.
- Step (a) is carried out for a time period in the range of 1 hour to 24 hours, and the stirring of resultant mixture in step (C) is carried out for a time period in the range of 1 hour to 48 hours.
- transition metal-Schiff base imine ligand complex can consist of any one of the combinations of the substituents selected from:
- Ri, R2, R3, R4, R6, R7, Rs, Rio, R 11 , and R 12 being hydrogen; R5, and R being tertiary butyl groups; M is Titanium (Ti); and X is CI; and
- Rj, R2, R3, R4, R6, Rs, Rio, and R 12 being hydrogen; R 5 , R 7 , R 9 , and R n being tertiary butyl groups; M is Titanium (Ti); and X is CI.
- the molar ratio of the aromatic diamine to the substituted salicylaldehyde of Formula-IIa is 1 : 1
- the molar ratio of the aromatic diamine to the substituted salicylaldehyde of Formula-IIb is 1 : 1.
- the molar ratio of the Schiff base imine ligand of Formula-Ill to the transition metal halide is 1 : 1.
- the transition metal-Schiff base imine ligand complex is used to produce disentangled ultrahigh molecular weight polyethylene having bulk density in the range of 0.03 g/cc to 0.2 g/cc; crystallinity in the range of 90 % to 99 %; fibrous and porous morphology; heat ( ⁇ ) of melting in the range of 180 J/g to 245 J/g; stretchability on softening; and molecular weight in the range of 0.1 to 12 million g/mole.
- Figure 1 illustrates the change in the elastic modulus of the DUHMWPE based polymer with time when tested by strain controlled rheometer using 8 mm parallel plate geometry.
- Figures 2A, 3 A, and 4A illustrate total ion chromatograms of catalyst 1, catalyst 2 and catalyst 3 respectively, as described in Table- 1 ;
- Figure 2B, 3B, and 4B illustrate mass spectra of catalyst 1, catalyst 2 and catalyst 3 respectively, as described in Table- 1 ;
- Figure 2C, 3C, and 4C illustrate expanded mass spectra of catalyst 1 , catalyst 2 and catalyst 3 respectively, as described in Table- 1 ;
- Figure 5 illustrates an XRD pattern of a disentangled ultra-high molecular weight polyethylene (DUHMWPE-1) obtained using the complex of the present disclosure as the catalyst 1.
- DHLMWPE-1 disentangled ultra-high molecular weight polyethylene
- Figure 6 illustrates a DSC thermograph of the DUHMWPE-1 obtained using the complex of the present disclosure as the catalyst 1.
- Figure 7 illustrates a SEM image of the DUHMWPE-1 obtained using the complex of the present disclosure as the catalyst 1.
- Figure 8 illustrates a SEM image of the DUHMWPE-2 obtained using the complex of the present disclosure as the catalyst 2.
- Figure 9 illustrates a SEM image of the DUHMWPE-3 obtained using the complex of the present disclosure as the catalyst 3.
- the present disclosure envisages a simple process to synthesize the catalyst by direct chelation of the Schiff base imine ligand using a transition metal halide.
- the process of the present disclosure can be easily scaled up to commercial scale.
- a process for preparing a transition metal-Schiff base imine ligand complex comprises following steps.
- each of Rj, R2, R 4 , R6, Rs, Rio, and Rj2 are independently selected from the group consisting of hydrogen, aryl, heteroaryl, and halogen;
- R5, and R are independently selected from tertiary alkyl groups
- R 7 , and Rn are independently selected from the group consisting of hydrogen, and tertiary alkyl group
- R3 is selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl, and sulphonic acid.
- the second product mixture is concentrated under reduced pressure to obtain a second residue comprising the crude transition metal-Schiff base imine ligand complex, followed by purification of the second residue using an organic fluid medium to obtain the transition metal-Schiff base imine ligand complex, represented by Formula-IV.
- each of Rj, R2, R 4 , R6, Rs, Rio, and Rj2 are independently selected from the group consisting of hydrogen, aryl, heteroaryl, and halogen;
- R5, and R9 are independently tertiary alkyl groups
- R 7 , and Rn are independently selected from the group consisting of hydrogen, and tertiary alkyl group;
- R3 is selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxyl, and sulphonic acid; M is a transition metal selected from the group consisting of Hafnium (Hi), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V), and Titanium (Ti); and
- X is a halide selected from the group consisting of CI, Br, and I.
- the aromatic diamine is meta- phenylenediamine.
- the substituted salicylaldehyde of Formula-IIa, and the substituted salicylaldehyde of Formula-IIb are independently selected from the group consisting of 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde.
- the substituted salicylaldehyde of Formula-IIa and the substituted salicylaldehyde of Formula-IIb can be same or different.
- the substituted salicylaldehyde of Formula-IIa, and the substituted salicylaldehyde of Formula-IIb is 3-tert- butylsalicylaldehyde.
- the acid catalyst is at least one selected from the group consisting of para-toluene sulfonic acid, and sulfuric acid. The acid catalyst accelerates the Schiff base formation as well as leads to complete product formation.
- the first fluid medium is at least one selected from the group consisting of toluene, methanol, ethanol, and xylene.
- the halogenated fluid medium is at least one selected from the group consisting of dichlorome thane, dichloroe thane, carbon tetrachloride, and chloroform.
- the halogenated fluid medium is dichloromethane.
- the transition metal halide is at least one selected from the group consisting of Hafnium (Hf) halide, Manganese (Mn) halide, Iron (Fe) halide, Rhenium (Re) halide, Tungsten (W) halide, Niobium (Nb) halide, Tantalum (Ta) halide, Vanadium (V) halide, and Titanium (Ti) halide.
- the halide is selected from the group consisting of chloride, bromide, and iodide.
- the transition metal halide is Titanium tetrachloride.
- the organic fluid medium is at least one selected from the group consisting of n-pentane, n- hexane, n-heptane, n-octane, and n-nonane.
- the organic fluid medium is n- hexane.
- the reaction medium and the reaction temperature play a crucial role in direct chelation of the Schiff base imine ligand with transition metal halide.
- step (a) is carried out for a time period in the range of 1 hour to 24 hours
- the stirring of resultant mixture in step (C) is carried out for a time period in the range of 1 hour to 48 hours.
- the transition metal-Schiff base imine ligand complex can consist of any one of the combinations of the substituents selected from: i. Ri, R2, R3, R4, R6, R7, Rs, Rio, R 11 , and Rj2 being hydrogen; R5, and R being tertiary butyl groups; M is Titanium (Ti); and X is CI; and
- Rj, R2, R 3 , R4, R6, Rs, Rio, and Rj2 being hydrogen; R5, R 7 , R9, and Rn being tertiary butyl groups; M is Titanium (Ti); and X is CI.
- the molar ratio of the aromatic diamine to the substituted salicylaldehyde of Formula-IIa is 1 :1
- the molar ratio of the aromatic diamine to the substituted salicylaldehyde of Formula-lib is 1 : 1.
- the molar ratio of the Schiff base imine ligand of Formula-Ill to the transition metal halide is 1 : 1.
- the chelation process of the present disclosure is carried out at an ambient temperature, ranging from 20 °C to 40 °C. Hence, the process of the present disclosure is easy to scale up at industrial scale as compared to the processes that are carried out at low temperature such as -78 °C.
- the chelation step of the process of present disclosure is carried out using less hazardous reagents. Further, the chelation step of the process of present disclosure employs mild reaction conditions. In contrast to conventional processes, the chelation process of the present disclosure does not use pyrophoric reagents such as n-butyl lithium, lithium diisopropylamide and the like. Therefore, the process of the present disclosure is simple, economical, and less hazardous.
- the catalytic activity of the transition metal-Schiff base imine ligand complex of the present disclosure is evaluated by a series of ethylene polymerization experiments using polymethylaluminoxane (PMAO) and/or methylaluminoxane (MAO) as co-catalyst.
- the ethylene polymerization is performed at ethylene pressure in the range of 0.1 bar to 20 bar and at a temperature of 0 °C to 60 °C for 1 hour to 10 hours to obtain dis-entangled ultra-high molecular weight polyethylene (DUHMWPE).
- the DUHMWPE obtained is characterized by at least one of the following properties:
- Step A Preparation of Schiff base imine ligand (Formula-IIIA) All operations were carried out under nitrogen atmosphere. 10.8 g of m-phenylene diamine (100 mmol), 34.2 ml of 3-tert butylsalicylaldehyde (200 mmol) and 50 mg of p-toluene sulfonic acid were dissolved in 250 ml of anhydrous toluene. The mixture was stirred at 110° C under nitrogen atmosphere for 5 hours to obtain a first product mixture.
- the first product mixture was concentrated under reduced pressure to obtain a first residue as a dark brown solid.
- Step B Direct chelation of the Schiff base imine ligand (Formula-IVA)
- Step B Direct chelation of the Schiff base imine ligand (Formula-IVA)
- Catalyst 1, catalyst 2, and catalyst 3 were characterized by mass spectroscopy and elemental analysis.
- Figures 2A, 3A, and 4A illustrate the total ion chromatograms of catalyst 1, catalyst 2 and catalyst 3 respectively.
- Figures 2B, 3B, and 4B illustrate the mass spectra of catalyst 1, catalyst 2 and catalyst 3 respectively.
- Figures 2C, 3C, and 4C illustrate the expanded mass spectra of catalyst 1 , catalyst 2, and catalyst 3 respectively.
- the structures of catalyst 1, catalyst 2, and catalyst 3 were confirmed by mass spectroscopy, and elemental analysis.
- Ethylene polymerization was performed in a glass reactor equipped with a stirrer, a temperature indicator, a pressure indicator, and feeding lines for catalyst, ethylene gas, and nitrogen.
- the glass reactor was charged with 500 mL of anhydrous hexane followed by addition of 1.6 ml of polymethylaluminoxane. 9 mg of titanium-Schiff base imine ligand complex (catalyst- 1) was added in the reactor to form active catalyst composition.
- Ethylene gas was charged in the reactor till a pressure of 6 bar was reached.
- the polymerization was carried out at 6 bar ethylene pressure, at 50 °C and at a speed of 1200 rpm for 3 hours.
- the reactor was depressurized and cooled to 30 °C.
- the slurry was filtered and polymer was dried under reduced pressure at 70 °C for 3 hours to obtain dis-entangled ultra-high molecular weight polyethylene (DUHMWPE-1).
- DUHMWPE-2 and DUHMWPE-3 were prepared by a process similar to experiment 2, using catalyst 2, and catalyst 3, respectively, instead of catalyst 1.
- Experiment 3 Preparation of Titanium-Schiff base imine ligand complex (hereinafter referred to as Comparative catalyst)
- a Titanium-Schiff base imine ligand complex was prepared by the process as mentioned below (hereinafter referred to as the comparative catalyst).
- the catalytic activity of the comparative catalyst was also evaluated in the same manner as the catalyst of the present disclosure.
- Step B Lithiation of Schiff base imine ligand followed by chelation with titanium tetrachloride
- the second mixture was allowed to warm to room temperature and was stirred for 3 hours to complete the lithiation reaction to obtain a third mixture.
- the third mixture was again cooled to -78 °C and 0.25 mL of titanium chloride (2.32 mmol) was added to it dropwise to obtain fourth mixture.
- the fourth mixture was allowed to warm to room temperature and was stirred for 15 hours to 18 hours to obtain a dark red brown mixture.
- the dark red brown mixture was concentrated under reduced pressure to obtain dark brown solid. 50 mL of dichloromethane was added to the dark brown solid and stirred for 5 minutes, and then filtered through a medium porosity G-2 sinter funnel.
- the filtration step was repeated twice using 50 mL of dichloromethane to remove all solid impurities from dark brown solid to obtain a filtrate.
- the filtrate was combined and dried under reduced pressure to obtain brown solids.
- the brown solids were then washed three times with 20 mL of n-hexane/diethyl ether (95:5) solution, followed by washing with n- hexane to obtain titanium-Schiff base imine ligand complex (Formula-IVA).
- DUHMWPE-1 The ethylene polymer obtained using catalyst 1, catalyst 2, and catalyst 3 is referred to as DUHMWPE-1, DUHMWPE-2, and DUHMWPE-3 respectively, whereas the ethylene polymer obtained by using the comparative catalyst is referred to as DUHMWPE-4.
- Table-1 summarizes the performance of the transition metal-Schiff base imine ligand complexes of the present disclosure and that of the comparative catalyst for ethylene polymerization.
- DUHMWPE prepared by experiments 1 to 3 were characterized by different analytical techniques such as X-ray diffraction (XRD), differential scanning calorimetry (DSC), and scanning electron microscope (SEM). The data is provided in Table-2.
- XRD X-ray diffraction
- DSC differential scanning calorimetry
- SEM scanning electron microscope
- Titanium-Schiff base imine ligand complex of the present disclosure exhibit excellent catalytic activity to polymerize ethylene and provides disentangled ultra-high molecular weight polyethylene (DUHMWPE) having high crystallinity, fibrous and porous morphology, high heat of melting, and stretchability on softening.
- DHMWPE disentangled ultra-high molecular weight polyethylene
- DUHMWPE-1 obtained by catalyst 1 showed two distinct peaks at 2 ⁇ of 21° and 24°, which correspond to the orthorhombic (110) and (200) planes respectively.
- the XRD analysis of DUHMPWE-1 indicates high degree of crystallinity in DUHMPWE-1.
- the XRD pattern of DUHMWPE-1 is depicted in Figure 5. DSC Analysis (to determine the melting point and ⁇ of melting of polymer samples)
- DSC of DUHMWPE-1 was carried out in the following manner.
- DUHMWPE-1 was heated under nitrogen atmosphere from 20° C to 180° C at a rate of 10° C/min, equilibrated for 3 min, and was subsequently cooled down to 20° C. After keeping the temperature constant at 20° C for 3 min, the sample was again heated to 180° C at a rate of 10° C/min. It was observed from DSC analysis ( Figure 6), that DUHMWPE-1 melts at 140.14 °C and the heat of melting is 203.4 J/g.
- Figure 7, 8, and 9 illustrates an SEM image which depicts fibrous and porous morphology of the DUHMWPE-1, DUHMWPE-2, and DUHMWPE-3 respectively. Because of porous nature, the bulk density of DUHMWPE-1, DUHMWPE-2, and DUHMWPE-3 is in the range of -0.03-0.2 g/cc as compared to the bulk density of -0.4 g/cc for normal UHMWPE.
- DUHMWPE-1, DUHMWPE-2, and DUHMWPE-3 obtained by the process of the present disclosure were identical in all aspects of DUHMWPE-4 obtained by the process of the prior art.
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CN201780008190.3A CN108699088B (zh) | 2016-01-25 | 2017-01-25 | 过渡金属席夫碱亚胺配体络合物制备工艺 |
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CN113307831B (zh) * | 2021-06-17 | 2023-08-22 | 安徽工业大学 | 一种钴(ii)香豆素类席夫碱配合物的制备方法及其应用 |
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CN102936301A (zh) * | 2012-11-07 | 2013-02-20 | 复旦大学 | 三齿席夫碱钛基烯烃聚合催化剂及其制备方法和应用 |
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